JPH058938B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to an agricultural polyolefin resin film with excellent weather resistance. ``Conventional technology'' Conventionally, polyolefin resin films such as polyvinyl chloride film, polyethylene film, and ethylene-vinyl acetate copolymer film have been mainly used as greenhouse covering materials used for temperature cultivation in agricultural greenhouses, tunnels, etc. ing. Among these, polyvinyl chloride film has been widely used in this field until recently because it has excellent weather resistance, transparency, toughness, heat retention, etc. On the other hand, polyolefin film does not contain plasticizers, does not cause soil contamination, does not generate harmful gases during incineration, is inexpensive, and has excellent processability, but this film has better weather resistance than polyvinyl chloride film. It has the disadvantage of poor performance. Therefore, although it has the above-mentioned advantages, it has not been used as a house covering film in the past. As a coating film with improved weather resistance of polyolefin resin film, as shown in JP-A-56-41254, a polyolefin resin containing a specific hindered amine light stabilizer and an inorganic fine powder having a specific polarity is used. Although it is known that this can be done, sufficient effects have not yet been obtained. "Problems to be Solved by the Invention" In view of the above-mentioned circumstances, the present inventors set out to obtain a polyolefin film that has excellent weather resistance without impairing the soil non-contaminating properties and incineration properties of the polyolefin film. As a result of intensive study, the present invention has been completed. "Means for Solving the Problems" The gist of the present invention is to add at least one specific organic phosphate metal salt compound represented by the following general formula [] and/or [] to 100 parts by weight of a polyolefin resin. An agricultural polyolefin resin film characterized by containing 0.1 to 5 parts by weight of each of the above compound and a hindered amine compound. (In the formula, M means zinc, calcium, barium, magnesium or strontium. Also, R ₁ , R ₂ and R ₃ are each alkyl, aryl, arylalkyl, alkylaryl or an alkyl group having an ether bond. ). The present invention will be explained in more detail below. The polyolefin resin in the present invention includes α-olefin homopolymers and copolymers with different monomers containing α-olefin as a main component, such as polyethylene, polypropylene, ethylene-propylene copolymers, Examples include ethylene-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Among these, low-density polyethylene with a density of 0.910 to 0.935, ethylene-α-olefin copolymer, and ethylene-vinyl acetate copolymer with a vinyl acetate content of 30% by weight or less have good transparency, weather resistance, and price. From this point of view, it is preferable as an agricultural film. Further, among these, ethylene-vinyl acetate copolymers having a vinyl acetate content of 5% by weight or more and 25% by weight or less are particularly preferred in terms of transparency, flexibility, weather resistance, etc. Examples of the alkyl group constituting the organophosphate metal salt compound represented by the general formula [] or [] include methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, sec-butyl, tertiary-butyl,
amyl, neopentyl, isoamyl, hexyl,
Isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl,
lauryl, tridecyl, _C12 - _C13 mixed alkyl,
stearyl, cyclopentyl, cyclohexyl,
Examples include cyclooctyl, cyclododecyl, 4-methylcyclohexyl, and the like. Examples of aryl groups include phenyl and naphthyl groups. Examples of arylalkyl groups include benzyl, β-phenylethyl,
Examples include α-phenylpropyl and β-phenylpropyl groups. Examples of alkylaryl groups include tolyl, xylyl, ethyl phenyl, butylphenyl, tertiary
Examples include butylphenyl, octylphenyl, isooctylphenyl, tertiary octylphenyl, nonylphenyl, 2,4-di-tertiary butylphenyl, and the like. Examples of the alkyl group having an ether bond include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl and α-methylfurfuryl, or
Methyl-, ethyl-, isopropyl-, butyl-, isobutyl-, hexyl-, cyclohexyl-, phenyl cellosolve residue; Methyl-, ethyl-, isopropyl-, butyl-, isobutyl carbitol residue; Triethylene glycol monomethyl ether , -monoethyl ether, -monobutyl ether residue; glycerin 1,2-dimethyl ether, -1,3-diethyl ether, -1-ethyl-2-propyl ether residue; nonylphenoxy polyethoxyethyl, lauroxy poly Examples include ethoxyethyl residues. The organic phosphate metal salt compounds having various substituents as described above can be blended singly or in combination of two or more. The blending amount shall be selected within the range of 0.1 to 5 parts by weight per 100 parts by weight of the polyolefin resin. If it is less than 0.1 part by weight, the weather resistance of the polyolefin resin film will not improve even if a hindered amine compound is used in combination. On the other hand, if the amount of the organic phosphate metal salt compound is more than 5 parts by weight, the transparency of the film will be extremely poor, which is not preferable. Within the above range, 0.2 to 2 parts by weight is particularly preferred. Among the metals, zinc, calcium and barium are particularly preferred. Structural formulas of the hindered amine compounds in the present invention include the following. (1) 2,2,6,6-tetramethylpiperidinyl-4-benzoate (2) Bis-(2,2,6,6-tetramethyl-4
-piperidinyl) sebacate (5) 1,3,8-triaza,7,7,9,9-tetramethyl-3-n-octyl-spiro[4,
5] Decane-2,4-dione (7) 1,2,3,4-tetra(4-carbonyloxy-2,2,6,6-tetramethylpiperidine)-butane (9) Tri-(4-acetoxy-2,2,6,6-
Tetramethylpiperidine)-amine (10) 4-acetoxy-2,2,6,6-tetramethylpiperidine (11) 4-stearoyloxy-2,2,6,6
-tetramethylpiperidine (12) 4-benzyloxy-2,2,6,6-tetramethylpiperidine (13) 4-(phenylcarbamoyloxy)-2,
2,6,6-tetramethylpiperidine (14) 4-(p-toluenesulfonyloxy)-
2,2,6,6-tetramethylpiperidine (15) Bis(2,2,6,6-tetramethyl-4
-piperidyl) terephthalate (16) Tris(2,2,6,6-tetramethyl-
4-piperidine) phosphite (17) 1,3,8-triaza-7,7,9,9-
Tetramethyl 2,4-dioxose spiro[4,
5] Decane (18) (2,2,6,6-tetramethylpiperidine)-4-spiro-2'-(6',6'-dimethylpiperidine)-4'-spiro-5''-hindantoin These hindered amine compounds may be used alone or in combination of two or more. The blending amount is within the range of 0.1 to 5 parts by weight, preferably 0.2 parts by weight per 100 parts by weight of the polyolefin resin.
It shall be selected within the range of ~2 parts by weight. The amount of compounding
If it is less than 0.1 part by weight, weather resistance will not improve even if an organic phosphate metal salt compound is used in combination. On the other hand, if the blended amount of the hindered amine compound is more than 5 parts by weight, the bloom (spraying out onto the surface of the film) after forming the film will be poor, and the effect of improving weather resistance will also be small. Further, the following compounding agents can be used in the film according to the present invention, if necessary. That is, plasticizers, organic phosphate esters, heat stabilizers, chelators, lubricants, antifogging agents (surfactants),
These include ultraviolet absorbers, infrared absorbers, antioxidants, antistatic agents, fillers, fungicides, algaecides, and colorants. As the plasticizer, those commonly used for plasticizing polyvinyl chloride, olefin-vinyl alcohol copolymers, etc. are used. Particularly preferred are polyhydric alcohols with a molecular weight of 250 or less, such as glycerin, ethylene glycol, triethylene glycol, and sorbitol. These also exhibit excellent effects in imparting antifogging properties, which are essential for agricultural films. Examples of these non-alcoholic plasticizers include phthalate esters such as dibutyl phthalate, heptyl phthalate, and di-2-ethylhexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, and methyl oleyl phthalate. Phthalic acid mixed group esters, dioctyl adipate, diisodecyl adipate,
Aliphatic dibasic acid esters such as dioctyl azelaate, glycol esters such as diethylene glycol dibenzoate, fatty acid esters such as butyl oleate, methyl acetyl ricinoleate, tricresyl phosphate, trioctyl phosphate,
Examples include phosphoric acid esters such as octyl diphenyl phosphate. Examples of organic phosphate esters that can be used include tricresyl phosphate (TCP), tricylenyl phosphate (TXP), dixylenyl monocresyl phosphate, monoxylenyl dicresyl phosphate, etc. Examples include phosphoric acid esters having one or more ethylphenols. Furthermore, it is also possible to use a phosphate ester produced by using a mixed alcohol whose raw material is xylenol, ethylphenol, and cresol as main components and using these alcohols in a specific ratio. The carboxylic acids constituting the metal salt of an organic acid used as a heat stabilizer in the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid, and linoleic acid. Acid, linoleic acid, neodecanoic acid, oleic acid, stearic acid, isodecanoic acid, isostearic acid, 12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, Brassic acid and similar acids and naturally occurring mixtures of the above acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, p-t- Butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, xylylic acid, ethylbenzoic acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid, monobutyl maleate, monodecyl phthalate, cyclohexanecarboxylic acid, etc. can be given. Phenols are also useful as organic acids.
For example, phenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, cyclohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethylphenol, poly(di-
penta)isopropylphenol, diisopropyl-m-cresol, butylphenol, isoamylphenol, isooctylphenol, 2-
Ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-t-octylphenol, di-t-nonyl Examples include phenol and di-t-dodecylphenol. Metal components include zinc, group a metals such as lithium, sodium, and potassium, and barium.
Group A metals such as calcium, magnesium, and strontium are included. Examples of lubricants that can be used include fatty acid lubricants such as stearic acid, palmitic acid, and myristic acid; fatty acid amide lubricants such as stearamide, palmitic acid amide, methylene bis stearamide, and ethylene bis stearamide; butyl stearate. , ester lubricants such as butyl palmitate, polyethylene wax, liquid paraffin, etc. Organic phosphite compounds used in the present invention as chelators include diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tributyl phosphite, Tris(dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl glycol)-1,4
-Cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, tris(lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris(2'-methyl-5'-tert-butyl-4'-oxyphenyl)butane diphosphite, tetra( _C12 - _C15 mixed alkyl)4,4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5
-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, tris(mono, dimixed nonylphenyl (phosphite, hydrogenated-4, 4'-isopropylidene diphenol polyphosphite, diphenyl bis[4,4'-n-butylidene bis(2
-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis(octylphenyl) bis[4,4'-n-butylidene bis(2
-tert-butyl-5-methylphenol)]-1,6
-Hexanediol diphosphite, phenyl-
4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4,
4'-n-butylidene bis(2-tert-butyl-5-
Methylphenol) diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, diphenyl tridecyl phosphite, phenyl di(tridecyl) phosphite, tris(2-cyclohexyl phenyl) ) Phosphite, ditridecyl di(2-cyclohexylphenyl) hydrogenated bisphenol A diphosphite, di(2,4-di-tert-butylphenyl)
Cyclohexylphosphite, 2,4-di-tertiary
Butylphenyl diisodecyl phosphite, tris(butoxyethoxyethyl) phosphite,
Examples include diphenyl acid phosphite, bis(2-cyclohexyl phenyl) acid phosphite, bis(2,4-di-t-butylphenyl) acid phosphite, bis(nonylphenyl) acid phosphite, dibenzyl acid phosphite, etc. It will be done. As the antifogging agent used in the present invention, nonionic, anionic and cationic surfactants are used, such as polyoxyalkylene ether,
Partial ester of polyhydric alcohol, partial ester of alkylene oxide adduct of polyhydric alcohol,
Examples include higher alcohol sulfate ester alkali metal salts, alkylaryl sulfonates, quaternary ammonium salts, and aliphatic amine derivatives. Specifically, polyoxyethylene lauryl ether, -stearyl ether, -nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, pentaerythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monostearate,
Sorbitan distearate, diglycerin monooleate, triglycerin diolate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, lauric acid Examples include basic pyridinium salts of laurylamide ethyl phosphate, triethylcetylammonium iodide, oleyl amino diethylamine hydrochloride, and dodecylpyridinium sulfate. Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.
-hydroxy-4-octoxybenzophenone,
2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-
Benzyloxybenzophenone, 2-hydroxy-4-methoxy-2'carboxybenzophenone,
2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2 ,2'-dihydroxy-4,4'-di-
Benzophenone UV absorbers such as methoxybenzophenone, 2,2'-dihydroxy-4,4'-di-methoxy-5-sulfobenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone ;2
-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert
-butylphenyl)benzotriazole, 2-
(2'-hydroxy-3',5'-dimethylphenyl)benzotriazole, 2-(2'-methyl-4'-hydroxyphenyl)benzotriazole, 2-
(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'- hydroxy-3′,
5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dimethylphenyl)-5-methoxybenzotriazole, 2
-(2'-n-octadecyloxy-3',5'-dimethylphenyl)-5-methylbenzotriazole,
2-(2'-hydroxy-5'-methoxyphenyl)
Benzotriazole, 2-(2'-hydroxy-
4′-octoxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-methoxyphenyl)-
5-Methylbenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5,6-dichlorobenzotriazole, 2-(2'-hydroxy-
5'-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-
tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-phenylphenyl)-5-chlorobenzotriazole, 2
-(2'-hydroxy-5'-dichlorohexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dichlorophenyl)benzotriazole, 2-(2'-hydroxy-4', 5'-dichlorophenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-
Chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5
-chlorobenzotriazole, 2-(2'-hydroxy-3'-methylphenyl)-5-butoxycarbonylbenzotriazole, 2-(2'-hydroxy-4',5'-dimethylphenyl) 5-butoxycarbonylbenzotriazole , 2-(2'-hydroxy)-5-ethoxycarbonylbenzotriazole, 2-(2'-acetoxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5-ethyl Sulfonebenzotriazole, 2-(2'-hydroxy-3',
5'-dimethylphenyl)-5-ethylsulfonebenzotriazole, 2-(2'-hydroxy-5'-
Phenylphenyl)benzotriazole, 2-
Benzotriazole UV absorbers such as (2'-hydroxy-5'-aminophenyl)benzotriazole; phenyl salicylate, p-tert-butylphenyl salicylate, p-methylphenyl salicylate, p-octylphenyl salicylate, etc. Examples include salicylic acid ester ultraviolet absorbers. Examples of phenolic antioxidants include 2,
6-di-tert-butyl-p-cresol, stearyl-(3,5-di-methyl-4-hydroxybenzyl)thioglycolate, stearyl-β-(4
-Hydroxy-3,5-di-tert-butyl phenyl)propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris(3',5'-di- tert-butyl-4'-hydroxybenzylthio)-1,3,
5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate, 2,2'-methylenebis(4-methyl-6-
tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-
methylenebis[6-(1-methylcyclohexyl)
p-cresol], bis[3,5bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,
2'-ethylidene bis(4,6-di-tert-butylphenol), 2,2'-ethylidene bis(4-tert-butylphenol)
butyl-6-tert-butylphenol), 1,1,
3-tris(2-methyl-4-hydroxy-5-
tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-
tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzyl isocyanurate, 1,3,5-tris(3 ,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,
6-diphenyl-4-octadecyloxyphenol, tetrakis[methylene-3-(3,5-di-
tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris(3,5-
di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris[(3,5-
di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-
Octylthio-4,6-di(4-hydroxy-
3,5-di-tert-butyl)phenoxy-1,3,
Phenols such as 5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol) and 4,4'-butylidenebis(2-tert-butyl-5-
Examples include polyhydric phenol carbonate oligoesters such as carbonate oligoesters (for example, polymerization degree of 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.) of methylphenol. Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl (e.g., glycerin, trimethylol, etc.). Examples include esters of ethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate (eg, pentaerythritol tetralaurylthiopropionate). Examples of the stabilizing aid used in the present invention include 2,6-di-t-butyl-p-cresol,
Dilaurylthiodipropionate, diphenylthiourea, phenyl indole, thiodiglycol bis(aminocrotonate), pentaerythritol, tris(hydroxyethyl)isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, dipentaerythritol adipate , pt-butylbenzoic acid, dehydroacetic acid, zinc dehydroacetate, nonylphenoxypolyethoxyphosphoric acid, benzoic acid, cinnamic acid, dibenzoylmethane, stearoylbenzoylmethane,
Examples include benzoylpentanoylmethane. Compounds that can be used as fungicides and algaecides include 2,4,5,6-tetrachloroisophthalonitrile, 10,10'-oxybisphenoxyarsine, 2-(4-thiazolyl)-benz Imidazole, N(fluorodichloromethylthio)phthalimide, N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)sulfamide, paraoxybenzoic acid ester, 5-bromo-5-nitro-
Examples include 1,3-dioxane, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 3-methyl-4-chlorophenol, N(tetrachloroethylthio)phthalimide, and tributyltin laurate. Examples of colorants that can be used include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, quinacridone, and carbon black. The above various resin additives can be used alone or in combination. The amount of the various resin additives mentioned above can be selected within a range that does not deteriorate the properties of the film, usually within a range of 5 parts by weight or less based on 100 parts by weight of the base polyolefin resin. To blend the phosphate compound, hindered amine compound, and other resin additives into the base polyolefin resin, weigh the necessary amounts of each and use a ribbon blender, Banbury mixer, super mixer, or other conventionally known compounding machine. , you can use a mixer. In order to form a film from the resin composition obtained in this way, a method known per se, such as a melt extrusion method (including a T-die method and an inflation method), a calender molding method, etc. can be used. You can follow the method provided. In addition, the film formed in this way has dustproof, fogproof, weatherproof, blocking and scraping resistance (specifically, the coating material is applied to the pipe section of the pipe house or the car wire holding section). A coating layer made of polyolefin resin may be provided on at least one surface of the film for the purpose of improving the film's resistance to damage caused by friction when opening and closing for ventilation or when being blown by the wind. do not have. The film according to the present invention may be transparent, satin finish, or semi-matte finish, and can be used for covering agricultural greenhouses (greenhouses), tunnels, etc.
It can also be used for mulching, bagging, etc. Also, regarding the thickness of the film, it is important to consider the strength and cost.
Preferably, those in the range of 0.03 to 0.3 mm, especially
Particularly preferred is one with a diameter of 0.05 to 0.2 mm. "Function" As described above, the present invention contains a specific amount of a specific organic phosphate metal salt compound and a hindered amine compound, so it is possible to obtain a polyolefin resin film with particularly excellent weather resistance. . "Examples" Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example Polyolefin resin 100 parts by weight Ethylene bisstearamide (lubricant)
0.1 part by weight Sorbitan monostearate (antifogging agent)
1.0 〃 2-Hydroxy-4-octoxybenzophenone (ultraviolet absorber) 0.1 〃 Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (antioxidant) 0.5 parts by weight (Ciba Geigy, product name IRGANOX-1076
The basic composition was 1), and the phosphate compounds and hindered amine compounds shown in Tables 1 to 3 were mixed therein in the proportions shown in Tables 1 to 3, and then tested at Banbury at a resin temperature of 130 to 150°C. After kneading for a minute, granulated pellets were produced using an extruder. The pellets thus obtained were subjected to T-die melt extrusion (200 DEG C.) to produce 20 types of films each having a thickness of 0.1 mm for each polyolefin resin. Table 1...Basic composition of polyolefin resins: high-pressure low-density polyethylene (manufactured by Mitsubishi Kasei, trade name Novatec F141: density = 0.924
Table 2: Basic composition of polyolefin resin: ethylene-vinyl acetate copolymer (manufactured by Mitsubishi Yuka, trade name Yucalon Eva EVA41H: vinyl acetate content = 15 wt%, density = 0.933 MI = 2
Table 3: Ionomer resin (manufactured by Mitsui Polychemicals, product name Himilan-1555: Sodium type, density = 0.95 MI = 10 g/10 min) was used as the polyolefin resin with the basic composition Hindered amine used in the examples The system compounds are of the following four types.・SANOL LS 770: Manufactured by Ciba Geigy, molecular weight 480.7, melting point 80-90℃・CHIMASSOR B 944LD: Manufactured by Ciba Geigy, molecular weight 2500 or less, melting point 100-135℃・MARK LA-57: Manufactured by Adeka Argus Chemical Co., Ltd. Melting point 60-140℃ - CYASORB UV 3346: manufactured by American Cyanamids, oligomer type, hindered amine, softening temperature 110 to 130°C. Each film obtained was evaluated according to the following method. The results are shown in Tables 1 to 3. Weather resistance test Each film was exposed on a window frame-shaped airtight test stand facing south and tilted at 45 degrees to the ground (installation location: Nagoya City, Aichi Prefecture), and some of the films were exposed periodically. was removed from the exposure test stand and evaluated for appearance and elongation. The evaluation criteria were as follows. ○...There is no change in appearance and the remaining elongation rate is 80% or more. ○×…No change in appearance, remaining elongation rate is 79-60%
Those within the range of. △: Appearance changes such as cracks and tears are partially observed, and the remaining elongation rate is in the range of 79 to 60%. Δx: Significant changes in appearance such as cracks and tears are observed, and the residual elongation rate is in the range of 59 to 40%. ×...Cracks are observed over the entire surface or the remaining elongation rate is less than 40%. Note that the residual elongation rate was calculated using the following formula. Remaining elongation rate (%) = Elongation after outdoor expansion / Elongation before outdoor expansion x 100 Transparency test Each film was pressed at a temperature of 180℃,
A laminated sheet with a thickness of 2m/m was created. The transparency of this sheet was visually evaluated as follows. ◎...good transparency ○...slightly turbid △...slightly white turbidity ×...poor transparency (considerably white turbidity) Blowout test After leaving the sample film in the room for 3 months, touch the surface with your finger. It was rubbed lightly, and the spouting condition was visually evaluated based on the extent of the marks as shown below. ◎ …No spewing (no marks left) ○…Almost no spewing (slight finger marks) △…Spraying but not very sticky ×…Clearly spewing and significant stickiness

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[Table] "Effects of the invention" As is clear from the examples and comparative examples above,
The film according to the present invention, that is, the film made of a polyolefin resin composition containing specific amounts of two essential components, a specific organic phosphate metal salt compound and a hindered amine compound, has excellent properties even when used outdoors for a long period of time. It has excellent weather resistance. It also has good transparency and little spouting.

Claims (1)

[Claims] 1 100 parts by weight of polyolefin resin at least one selected from specific organic phosphate metal salt compounds represented by the following general formula [] and/or [].
An agricultural polyolefin resin film comprising 0.1 to 5 parts by weight of each of a seed compound and a hindered amine compound. (In the formula, M means zinc, calcium, barium, magnesium or strontium. Also, R ₁ , R ₂ and R ₃ are each alkyl, aryl, arylalkyl, alkylaryl or an alkyl group having an ether bond. )